An ideal solid oxide fuel cell (SOFC) cathode should meet multiple requirements, i.e., high activity for oxygen reduction reaction (ORR), good conductivity, favorable stability, and sound thermo‐mechanical/chemical compatibility with electrolyte, while it is very challenging to achieve all these requirements based on a single‐phase material. Herein, a cost‐effective multi‐phase nanocomposite, facilely synthesized through smart self‐assembly at high temperature, is developed as a near‐ideal cathode of intermediate‐temperature SOFCs, showing high ORR activity (an area‐specific resistance of ≈0.028 Ω cm² and a power output of 1208 mW cm⁻² at 650 °C), affordable conductivity (21.5 S cm⁻¹ at 650 °C), favorable stability (560 h operation in single cell), excellent chemical compatibility with Sm_0.2Ce_0.8O_1.9 electrolyte, and reduced thermal expansion coefficient (≈16.8 × 10⁻⁶ K⁻¹). Such a nanocomposite (Sr_0.9Ce_0.1Fe_0.8Ni_0.2O_3–δ) is composed of a single perovskite main phase (77.2 wt%), a Ruddlesden–Popper (RP) second phase (13.3 wt%), and surface‐decorated NiO (5.8 wt%) and CeO₂ (3.7 wt%) minor phases. The RP phase promotes the oxygen bulk diffusion while NiO and CeO₂ nanoparticles facilitate the oxygen surface process and O²⁻ migration from the surface to the main phase, respectively. The strong interaction between four phases in nanodomain creates a synergistic effect, leading to the superior ORR activity.